Detergent composition

ABSTRACT

A detergent composition comprises, by weight, (a) a major proportion of a mono- or di-alkyl aryl sulphonate in which the (or one) alkyl group has at least 8, preferably 8-16, carbon atoms, and the other alkyl group (if present is methyl, and (b) a minor proportion of (i) an alkyl aryl sulphonate in which the (or each)) alkyl group contains 0-7 carbon atoms, the sum of the carbon atoms in all the alkyl groups present being preferably less than 8, (ii) a condensate of not more than 11, and preferably 7-10, molar proportions (average) of alkylene oxide with an alcohol, a phenol or a mercaptan, and (iii) a condensate of more then 11, preferably 11-18, molar proportions (average) of alkylene oxide with an alcohol, a phenol or a mercaptan; (a) normally comprises 55-80%, preferably 60-70%, (b) (i) usually amounts to 1-17.5%, preferably 5-12.5%, (b) (ii) to 10-30%, preferably 15-25%, and (b) (iii) to 1-17.5%, preferably 5-12.5%; (a) is most suitably a mixture of C8-13-straight chain monoalkyl benzene sulphonates, and (b) (i) is suitably a toluene, xylene, benzene or naphthalene sulphonate; in (a) and (b) (i) the cation present is generally alkali metal, ammonium or alkanolamine, sodium and potassium being preferred.  The alkylene oxide condensates (b) (ii) and (iii) are normally derived from C2-4-alkylene oxides, and especially from ethylene oxide, and from C6-20-aliphatic alcohols, C4-10-alkyl phenols, especially octyl phenol, and C6-20-tertiary aliphatic mercaptans. The composition may in addition contain up to 10% urea, and also alkali metal phosphates and polyphosphates, sodium silicate and carboxymethylcellulose, and may be produced as an aqueous solution comprising 20-60% of the composition.  Specification 870,457 is referred to.

United States Patent 3,140,261 DETERGENT COMPOSITION Reginald W. Noad,Sutton, England, assignor to Shell Oil Company, New York, N.Y., acorporation of Delaware No Drawing. Filed Nov. 13, 1961, Ser. No.152,015 Claims priority, application Great Britain Nov. 15, 1960 2Claims. (Cl. 252-161) The present invention relates to detergentcompositions containing alkyl aryl sulphonates.

According to the present invention the detergent composition comprises amajor proportion by weight of a mono alkyl aryl sulphonate in which thealkyl group containsat least 8 carbon atoms or a di-alkyl arylsulphonate in which one of the alkyl groups is methyl and the otheralkyl group contains at least 8 carbon atoms, and a minor proportion byweight of (i) an alkyl aryl sulphonate in which the or each alkyl groupcontains less than 8 carbon atoms (and preferably in which the sum ofcarbon atoms in the alkyl groups is less than 8) or an aryl sulphonate,(ii) a phenol-alkylene oxide condensate, an alcohol-alkylene oxidecondensate or a mercaptan-alkylene oxide condensate having an average ofnot more than 11 alkylene oxide units per molecule, and (iii) aphenolalkylene oxide condensate, an alcohol-alkylene oxide condensate,or a mercaptan-alkylene oxide condensate having an average of more than11 alkylene oxide units per molecule. Such a detergent composition whendissolved in Water has a high foaming performance, good stability at lowtemperatures, and has a viscosity which is not appreciably dependent onconcentration.

The monoor di-alkyl aryl sulphonate which constitues the majorproportion by weight of the detergent composition is preferably asulphonic acid or a salt thereof, of an alkylated benzene or toluene,although those of naphthalene may equally well be used. The salts mayfor example be alkali metal such as sodium or potassium salts, orbeammonium or alkanolamine salts. Examples of sulphonates of this type arethe alkali metal salts of sulphonic acids such as are obtained byalkylating benzene or toluene, with an alkylating agent havingpreferably between eight and sixteen carbon atoms inclusive permolecule, for an example an olefin, an olefin polymer or alkyl halide,and converting the alkyl aromatic hydrocarbon thus formed into thecorresponding mono-sulphonic acid. The sulphonic acids may then bereadily neutralised by. adding for example alkali metal hydroxide oralkali metal carbonate to form the corresponding salts. In this manner,mono or di-primary alkyl aryl sulphonates, secondary alkyl arylsulphonates, or keryl benzene sulphonates can be readily obtained.Sulphonic acids or salts thereof, in which the alkyl group containsbetween group contains less than 8 carbon atoms, and preferably in whichthe sum of the carbon atoms in the alkyl group or groups is less than 8are chemically similar to and may be prepared by similar methods tothose monoor di-alkyl aryl sulphonates described above. They may ofcourse be polyalkyl aryl sulphonates e.g. xylene sulphonates. Othersuitable sulphonates include monoand poly-propyl, butyl, amyl or heptylbenzene sulphonates, propylated naphthalene sulphonates or butylateddiphenyl sulphonates. The alkyl aryl sulphonic acid salts, particularly3,146,261 Patented July 7, 1964 alkali metal or ammonium salts arepreferred e.g. the

V potassium xylene sulphonates or sodium toluene sulphonates.

The aryl sulphonates may be obtained by sulphonation of the arylhydrocarbon e.g. by sulphonation of benzene or naphthalene to form abenzene or naphthalene sulphonate. The sulphonic acids thereby formedmay be neutralised to form the corresponding salts, e.g. alkali metal,ammonium or alkanol-amine salts. Examples of such salts are sodium orpotassium benzene sulphonates.

If desired, instead of blending together the short chain alkyl arylsulphonate or aryl sulphonate with the longer chain monoor di-alkyl arylsulphonate and the other components of the detergent composition of theinvention, the desired blend of sulphonates may be prepared bysulphonating directly a mixture of short chain alkylated arylhydrocarbon or aryl hydrocarbon with the longer chain monoor di-alkylaryl hydrocarbon. Thus, a mixture of straight chain (C to C mono alkylhydrocarbon and xylene or toluene may be sulphonated using for exampleS0 in a SO /a1kylate mole ratio about 3:1.

The alkylene oxide/phenol, alkylene oxide/ alcohol or alkyleneoxide/mercaptan condensates used in compositions of the presentinvention may be derived from any alkylene oxide, but preferably fromalkylene oxides containing between two and four carbon atoms in themolecule inclusive. The preferred alkylene oxides are ethylene oxide or1,2-propylene oxide. Other suitable alkylene oxides are 1,2- and2,3-butylene oxides, and isobutylene oxide. Any method suitable for thepreparation of these condensates can be used, and one such method isdeand subsequently treating with a lower aliphatic alcohol or glycol andremoving the suspended solid material and the alcohol or glycol from thepolyoxyalkylene compound.

Alkylene oxide/ phenol and alkylene oxide/ alcohol condensates may alsobe prepared using mixtures of alkylene oxides. Thus, for example, if amixture of ethylene oxide and 1,2-propylene oxide is employed, apolyoxyalkylene compound is formed in which the ethylene oxide andpropylene oxide units are distributed randomly throughout thepolyoxyalkylene compound in substantially the same proportions as thealkylene oxides are present in the mixture used. Alternatively, twodifferent alkylene oxides may be used alternately, or several differentalkylene ox= ides may be used successively so giving block copolymers.

. One method of making these block copolymers is by condensing anorganic compound containing at least one hydroxyl group e.g. a phenol oran alcohol, at an elevated temperature and in the presence of acondensation catalyst, with one or more equivalents of an alkyleneoxide.

subsequently with one or-more equivalents or an alkylene oxide differentfrom the first alkylene oxide, and then with one or more equivalents ofan alkylene oxide dilferent from the second alkylene oxide.v Suitablecondensation catalyst are strong bases, e.g. a quaternary ammomum baseor sodium hydroxide, orcompounds such as boron taining an average'of notmore than 11 alkylene oxide" units per molecule, and condensatescontaining an aver-:

age of more than 11 alkylene oxide units per molecule may be readilyprepared. Particularly preferred condensates are respectively, thosecontaining an average of between 7 and 10 moles of alkylene oxide permole of phenol, alcohol, or mercaptan e.g. an average of 8.5 moles ofalkylene oxide per mole of phenol, alcohol or mercaptan, and thosecontaining an average of between 11 and 18 moles of alkylene oxide permole of phenol, alcohol or mercaptan e.g. an average of 15 moles ofalkylene oxide per mole of phenol, alcohol, or mercaptan.

The phenols from which the alkylene oxide/phenol condensates are derivedinclude phenol itself, the cresols, resorcinol and the alkyl and dialkylphenols. Preferred phenols are the alkyl phenols, and these aregenerally prepared by alkylating phenol with an olefin containing thedesired number of carbon atoms. Preferred alkyl phenols are those inwhich the alkyl group contins between 4 and 10 carbon atoms inclusive,and a particularly preferred alkyl phenol is octyl phenol. Anothersuitable phenol is dodecyl phenol.

The alcohols from which the alkylene oxide/alcohol condensates arederived, include monohydric primary, secondary or tertiary alcohols,preferably those having between 6 and 20 carbon atoms inclusive in themolecule and more preferably between 12 and 18 carbon atoms inclusive inthe molecule. Preferably aliphatic alcohols, for example, laurylalcohol, cetyl alcohol, oleyl alcohol and 2-ethyl hexanol are used butarylalkyl alcohols, for example benzyl alcohol or the alkyl benzylalcohols can be used.

Similarly, the mercaptan/alkylene oxide condensates may be derived fromprimary, secondary, or especially tertiary mercaptans. Preferably themercaptan has between 6 and 20 carbon atoms inclusive per molecule,especially between 12 and 18 carbon atoms inclusive per molecule. Themercaptan may be an aralkyl mercaptan, but aliphatic mercaptans arepreferred. Examples of suitable mercaptans are the primary, secondary ortertiary dodecyl or octadecyl mercaptans.

Phenol condensates particularly alkyl phenol condensates are preferredto alcohol or mercaptan condensates and the particularly preferredcondensates are respectively a condensate of octyl phenol and ethyleneoxide containing an average of 8.5 ethylene oxide units per molecule anda condensate of octyl phenol and ethylene oxide containing an average of15 ethylene oxide units per molecule.

As with the monoor di-alkyl aryl sulphonate constituting the majorproportion of the detergent composition, mixtures of each of the threecomponents (which together constitute the minor proportion of thedetergent composition) may be used.

The proportion by weight of monoor di-alkylaryl sulphonate may varyprovided of course it is a major proportion by weight. However, thepreferred proportion by weight is between 55% and 80%, especiallybetween 60% and 70% e.g. about 65%.

Similarly the proportions of the other components may vary provided theytogether constitute a minor proportion of the composition of theinvention. Thus, a proportion by weight of between 10% and 30%,especially between 15% and 25% e.g. about 20%, is preferred for thephenol-, alcoholor mercaptan-alkylene oxide condensate having an averageof not more than 11 alkylene oxide units per molecule. The proportion byweight of each of the two other components (i.e. the alkyl arylsulphonate in which the or each alkyl group has less than 8 carbon atomsor the aryl sulphonate and the phenol-, alcoholor mercaptan-alkyleneoxide condensate having an average of more than 11 alkylene oxide unitsper molecule) is preferably between 1% and 17.5%, particularly betweenand 12.5% e.g. about 8.5%.

In order to reduce the clear point of the resultant blend, additiveswell-known for this purpose, e.g. urea, may be added to the blend.Usually no more than by weight e.g. about 5% by weight of the detergentactive matter, need be added.

Detergent compositions of the invention are more conveniently sold inaqueous solution. Thus a suitable aqueous solution preferably containsbetween 20% and 60% by Weight of the detergent composition, for exampleabout 40% by weight.

Detergent compositions of the present invention may include the usualbuilders provided the use of such materials does not adversely affectthe desired properties. These builders include for example the watersoluble alkali metal phosphates, the polyphosphate salts, sodiumsilicate, and sodium carboxymethyl cellulose. The builders may be addedeither before or after dilution of the detergent composition, butpreferably after dilution.

EXAMPLE I A detergent composition was prepared by mixing 23.8% by weightof sodium (C to C monoalkyl benzene sulphonates, 3.4% by weight ofpotassium xylene sulphonate, 7.1% by weight of octyl phenol-ethyleneoxide condensate containing an average of 8.5 ethylene oxide units permolecule, and 3.1% by weight of octyl phenol-ethylene oxide condensatecontaining an average of 15 ethylene oxide units per molecule, theremainder comprising water.

This composition was found to have good foam stability as determined ina Dish-Washing Test. It also showed good viscosity/dilutioncharacteristics, and good stability when stored at low temperatures.

EXAMPLE II Straight chain (C to C monoalkyl benzenes were oleumsulphonated using a SO /alkylate mole ratio of 3.5:1 and a residencetime of 2 minutes. The sulphonic acids were then neutralised withaqueous sodium hydroxide, and the resulting solution of sodiumsulphonates were desalted so that the final sodium alkyl benzenesulphonates had an inorganic salt content of about 2.0% by weight onactive matter.

70 parts by weight of the thus prepared sodium (C to C alkyl benzenesulphonates were then mixed with 9 parts by weight of octylphenol-ethylene oxide condensate having an average of 15 ethylene oxideunits per molecule and 21 parts by weight of octyl phenol-ethylene oxidecondensate having an average of 8.5 ethylene oxide units per molecule.

To the three-component blend thus obtained 10 parts by weight of shortchain alkyl aryl sulphonate was then added. The four-component blend wasthen diluted to different active matter concentrations and the viscosityand clear points determined. Using four different short chain alkyl arylsulphonates comparative figures were obtained.

In this and following examples Na/T=sodium toluene sulphonate,Na/X=sodium xylene sulphonate, K/T: potassium toluene sulphonate andK/X=potassium xylene sulphonate. Also, in this and the followingexamples the term detergent active matter does not include the shortchain alkyl aryl sulphonate.

EXAMPLE III Exactly the same procedure as Example II was carried outexcept that the sO /alkylate mole ratio was 2.821, and the residencetime was 30 minutes.

The figures for the viscosities and clear points were as follows.

Mixed feedstocks of straight-chain (C to C monoalkyl benzenes withtoluene or xylene were prepared which would give sodium toluene orsodium xylene sulphonate on the total active matter in the finishedblend with the non-ionics. These mixtures were then sulphonated using aSO /alkylate mole ratio of 2.921 and a residence time of 25 minutes. Thereaction mixtures were then de-acidified, neutralised, desalted andde-oiled.

To 80 parts by weight of each of these blends 9 parts by weight of octylphenol-ethylene oxide condensate having an average of ethylene oxideunits per molecule and 21 parts by weight of octyl phenol-ethylene oxidecondensate having an average of 8.5 ethylene oxide units per moleculewere added.

The finished blends were then diluted with water to different activematter concentrations and the viscosities and clear points determined.The results were as follows. a

Detergent Blend con- Blend conactive taining taining Analysis mattersodium sodium percent toluene xylene wt. sulphonate sulphonateViscosity, cs. at C 34 291 258 30 229 241 227 224 20 232 184 15 117 68Clear point, C 34 17.0 2.0 9. 5 -l. 0 25 4.0

Comparative Test By way of comparison, the blends of Examples II, IIIand IV but omitting the fourth component i.e., the Na/T, Na/X, K/T, orK/X, were diluted to equivalent active matter concentrations and theviscosities and clear points determined.

The equivalent comparative blends to those of Examples II, III and IVare denoted by A, B and C.

Thus, at active matter concentrations of below 20% wt., e.g. at 15 or17% wt. the compositions of the invention, especially those containingpotassium toluene sulphonate, usually have higher viscosities than thoseof blends A, B or C above. the compositions of the invention at higherconcentrations are not as high as those of blends A, B and C.

EXAMPLE V To blends of parts by weight of sodium (C to C monoalkylbenzene sulphonates with 9 parts by weight of octyl phenol-ethyleneoxide condensate having an average of 15 ethylene oxide units permolecule, and 21 parts by weight of octyl phenol-ethylene oxidecondensate having an average of 8.5 ethylene oxide units per moleculewere added 8, 10 or 12 parts by weight of sodium toluene sulphonate.

The viscosities and clear points of the resultant blends diluted todifferent aqueous concentrations were as fol- A blend of 70 parts byWeight of sodium (C to C monoalkyl benzene sulphonates, 27 parts byweight of octyl phenol-ethylene oxide condensate having an average of8.5 ethylene oxide units per molecule, 3 parts by weight of octylphenol-ethylene oxide condensate having an average of 15 ethylene oxideunits per molecule, and 10 parts by weight of potassium Xylenesulphonate was prepared.

This blend was diluted with water to various concentrations and theviscosities determined. 5% and 10% by weight based on the active matterof urea was also added, the corresponding viscosities at differentdilutions determined. The clear points at 35% detergent active matterdilutions were also determined.

The results were as follows:

Detergent compositions which have good detergent properties combinedwith good foaming characteristics and a low critical solutiontemperature are made by mixing the following components in aqueoussolution in the proportions indicated in the following table where thepercentages are by weight of the aqueous detergent solution.

In addition, the viscosities of Percent by weight Detergent compositionLauryl alcohol-ethylene and propyleneoxide condensate, average 8oxyalkylene units per molecule Alkylene oxide condensate, average morethan 11 oxyalkylene units per molecule:

See. bu tyl phenol-propylene oxide condensate, average 11 oxyalkylcneunits per molecule Nonyl phenol-ethylene oxide condensate,

average 17 oxyalkylene units per moleper molecule Water A similar gooddetergent is obtained by substituting corresponding amounts of dodecylmercaptan-ethylene oxide condensates having an average of 8.5 and 16oxyethylene units per molecule respectively for the condensates ofcomposition A.

I claim as my invention:

1. A detergent composition having good detersive and viscosity dilutionproperties consisting essentially of water and from to 60% of solute,said solute consisting essentially of (a) 60 to 70% by Weight of alkalimetal alkyl aryl sulfonates selected from the group consisting of alkylbenzene sulfonate and alkyl toluene sulfonate having 8 to 13 alkylcarbon atoms,

(b) 5 to 12.5% by weight of alkali metal alkyl aryl sulfonates selectedfrom the group consisting of toluene sulfonate and xylene sulfonate,

(c) 15 to 25% by Weight of a polyethylene oxide ether and alkyl phenolcondensate having 7 to 10 ethylene oxide units per molecule and 4 to 10alkyl carbon atoms, and

(d) 5 to 12.5% by weight of a polyethylene oxide ether and alkyl phenolcondensate having 11 to 18 ethylene oxide units per molecule and 4 to 10alkyl carbon atoms.

2. A detergent composition having good detersive and viscosity dilutionproperties consisting essentially of water and from 20 to of solute,said solute consisting essentially of (a) 60 to by Weight of sodiumalkyl aryl sulfonates selected from the group consisting of alkylbenzene sulfonate and alkyl toluene sulfonate having 8 to 13 alkylcarbon atoms,

(b) 5 to 12.5% by Weight of alkali metal alkyl aryl sulfonates selectedfrom the group consisting of toluene sulfonate and xylene sulfonate,

(c) 15 to 25% by weight of a polyethylene oxide ether and octyl phenolcondensate having an average of 8.5 ethylene oxide units per molecule,and

(d) 5 to 12.5% by weight of a polyethylene oxide ether and octyl phenolcondensate having an average of 15 ethylene oxide units per molecule.

References Cited in the file of this patent UNITED STATES PATENTS

1. A DETERGENT COMPOSITION HAVING GOOD DETERSIVE AND VISCOSITY DILUTIONPROPERTIES CONSISTING ESSENTIALLY OF WATER AND FROM 20 TO 60% OF SOLUTE,SAID SOLUTE CONSISTING ESSENTIALLY OF (A) 60 TO 70% BY WEIGHT OF ALKALIMETAL ALKYL ARYL SULFONATES SELECTED FROM THE GROUP CONSISTING OF ALKYLBENZENE SULFONATE AND ALKYL TOLUENE SULFONATE HAVING 8 TO 13 ALKYLCARBON ATOMS, (B) 5 TO 12.5% BY WEIGHT OF ALKALI METAL ALKYL ARYLSULFONATES SELECTED FROM THE GROUP CONSISTING OF TOLUENE SULFONATE ANDXYLENE SULFONATE, (C) 15 TO 25% BY WEIGHT OF A POLYUETHYLENE OXIDE ETHERAND ALKYL PHENOL CONDENSATE HAVING 7 TO 10 ETHYLENE OXIDE UNITS PERMOLECULE AND 4 TO 10 ALKYL CARBON ATOMS, AND (D) 5 TO 12.5% BY WEIGHT OFA POLYETHYLENE OXIDE ETHER AND ALKYL PHENOL CONDENSATE HAVING 11 TO 18ETHYLENE OXIDE UNITS PER MOLECULE AND 4 TO 10 ALKYL CARBON ATOMS.